JPH06161097A - Photosensitive resin composition for sand blasting and laminated film formed by using the same - Google Patents

Abstract

PURPOSE:To provide the photosensitive resin compsn. for sand blasting which is greatly improved in blast resistance performance and the laminated film formed by using this compsn. CONSTITUTION:This photosensitive resin compsn. is prepd. by mixing cellulose phthalate acetate into urethane acrylate, and adding and dissolving 2,4,6- trimethyl benzoyl diphenyl sulfoneoxide, N-nitrosophenyl hydroxylamine aluminum salt and 'Oil blue-613(R)' to and in this mixture. A water-soluble resin soln. separately prepd. by adding polyethylene glycol to polyvinyl alcohol and stirring and mixing the mixture is applied on a PET film 1 to form a water-soluble resin layer 2. Further, the photosensitive resin compsn. is applied thereon to form a photosensitive resin compsn. layer 3 and finally a release film 4 is put and integrated thereon, by which the dry film is formed.

Description

Detailed Description of the Invention

[0001]

The present invention relates to glass, ceramics,
On the surface of stone, wood, ceramics, plastic, etc., letters,
The present invention relates to a photosensitive resin composition for sandblasting and a laminated film using the same for efficiently engraving photographic images, patterns and the like.

[0002]

2. Description of the Related Art Conventionally, as a method of forming an image by sandblasting on the surface of glass, ceramics, stones, etc., a rubber plate, paper, etc. is attached to the surface of a base material, cut out with a cutter etc., patterned and then sandblasted. It is known that the resist ink is pattern-printed and dried by a screen printing method, and then sandblasting is performed.

Further, JP-A-60-10242 discloses a screen-curable photocurable resin for sandblasting, which contains a urethane prepolymer having an ethylenically unsaturated group at a terminal and a monofunctional ethylenically unsaturated compound. Compounds are disclosed. Further, JP-A-60-104938 and JP-A-6-104938
Japanese Patent Laid-Open No. 0-104939 also discloses a transfer material for sandblasting, which contains an unsaturated polyurethane having an ethylenically unsaturated group at the terminal and an ethylenically unsaturated compound.

In addition to the above, Japanese Patent Application Laid-Open No. 2-69754 discloses a photosensitive laminated film (dry film) for an engraving mask in which a water-developable photosensitive resin composition and a photosensitive adhesive composition are laminated together. Is proposed.

[0005]

However, the above-mentioned rubber,
The method of cutting out a paper or the like with a cutter is complicated and time-consuming, and there is a problem that work efficiency is not improved. Further, when an image mask made of a photosensitive resin containing a polyurethane resin and a monofunctional ethylenically unsaturated compound is transferred, it is difficult to handle and control the film thickness because the photosensitive composition is liquid, and the resolution and There is a drawback that the degree of adhesion with the material to be engraved is not sufficient. Further, with respect to the above-mentioned photosensitive laminated film for engraving mask, since the developing solution is water, safety in work is secured. When performing deep blast etching, the wear of the resist is severe. Therefore, when trying to thicken the resist film, especially 100 μm
In the above case, the diazo resin or the like is thermally decomposed during drying, which makes it difficult to prepare, and the formed photosensitive film mask has a low grade. Further, since transfer is performed using an adhesive, it is not suitable when precision of electronic parts and the like is required.

[0006]

In order to solve the above problems, in the present invention, a urethane oligomer having an ethylenically unsaturated double bond at the terminal and a cellulose derivative or a compound having an ethylenically unsaturated double bond are provided. By using 2,4,6-trimethylbenzoyldiphenylphosphine oxide as a photopolymerization initiator in the contained photosensitive resin composition, the workability is good, and the resolution and the degree of adhesion to the engraved material are sufficient. Further, the present invention provides a photosensitive resin composition having a wide exposure range and excellent abrasion resistance during sandblasting.

A water-soluble resin layer, a photosensitive resin composition layer, and a release film are laminated in this order on a flexible film using the above-mentioned photosensitive resin composition layer for sandblasting containing a cellulose derivative. The present invention also provides a photosensitive laminated film for sandblasting, which has excellent workability.

2, as the photopolymerization initiator according to the present invention
4,6-Trimethylbenzoyldiphenylphosphine oxide is sold under the trade name of "Lucirin TPO" by BASF, for example, and is a photosensitive resin composition 1
0.05 to 20 parts by weight, more preferably 0.
It is preferable to add 5 to 10 parts by weight. It is not clear why the above remarkable effect can be achieved only when this photopolymerization initiator is used, but it absorbs a wavelength in the ultraviolet region and photocrosslinks a compound having an ethylenically unsaturated double bond. It is presumed to be effective.

The urethane oligomer having an ethylenically unsaturated double bond at the terminal according to the present invention is reacted with a polyol component and an isocyanate component in an excess of isocyanate groups to form a prepolymer having a terminal NCO, which has a hydroxyl group-containing group. It can be formed by reacting a compound having an ethylenically unsaturated double bond to form an oligomer having a molecular weight of 30,000 or less.

Examples of the above-mentioned polyol component are reaction of polyether polyols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, diols such as ethylene glycol and diethylene glycol with dibasic acids such as adipic acid and phthalic anhydride. The polyester polyols obtained by Examples of the isocyanate component include 2,4-
Toluene diisocyanate, 2,6-toluene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate and the like can be mentioned.

Examples of the compound having a hydroxyl group-containing ethylenically unsaturated double bond include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 2-hydroxyethyl methacrylate.
Examples thereof include hydroxypropyl acrylate, 2-hydroxypropyl methacrylate and the like, or those obtained by reacting these with ε-caprolactone and the like, and further esterification products of the above polyols with acrylic acid and methacrylic acid.

The cellulose derivative according to the present invention is contained in a photosensitive resin composition suitable for forming the above-mentioned laminated film, has good compatibility with the urethane oligomer, and is used as an engraved material. It satisfies requirements such as good adhesiveness with, good peelability from the flexible film, and easy removal with a developing solution. As such a cellulose derivative, one having a carboxyl group is preferable, and cellulose acetate phthalate is particularly preferable. This cellulose derivative is
10 to 1 based on 100 parts by weight of the urethane oligomer
It is preferable to add 00 parts by weight.

Further, the compound having an ethylenically unsaturated double bond according to the present invention is photopolymerized by an active light source in the presence of a photopolymerization initiator and becomes insoluble in a developing solution. Examples of the compound include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, benzyl acrylate, benzyl methacrylate, phenoxy acrylate, phenoxy methacrylate, isobornyl acrylate, isobornyl methac Rate, and the like. It is preferable to add 10 to 200 parts by weight of the compound having an ethylenically unsaturated double bond to 100 parts by weight of the urethane oligomer. Further, in the above photosensitive resin composition, as other components, a polymerization inhibitor, a plasticizer,
Conventionally known materials such as dyes and pigments can be appropriately used as necessary.

The photosensitive resin composition for sandblasting of the present invention is applied by a method of forming a photosensitive resin layer by coating it on a material to be engraved in a liquid state according to the use as described above, or by a screen printing method. It can be used for both the method of forming and the method of forming a photosensitive resin layer on a flexible film in advance and drying it and then sticking this film on an engraved material (dry film method). it can. By using these methods, it is possible to form a resin pattern at an accurate position because it is not necessary to transfer a resin pattern formed in advance when precise alignment of electronic parts or the like is required, and high precision is achieved. Can be etched.

FIG. 1 shows an example of a dry film. The water-soluble resin layer 2 is applied on the flexible film 1, and the photosensitive resin composition layer 3 of the present invention is formed thereon. Further, a release film 4 is placed on and integrated therewith.

Since the film 1 supports the photosensitive resin composition layer 3 of the present invention and needs to have appropriate flexibility, a polyethylene terephthalate (PET) film having a thickness of 16 to 125 μm is preferable, In addition to this, synthetic resin films such as polyethylene, polypropylene, polycarbonate and polyvinyl chloride can be used.

The water-soluble resin layer 2 is for preventing the oxygen desensitizing action of the photosensitive resin and for preventing the adhesion of the mask pattern at the time of exposure, and needs to be water-soluble so that it can be removed by the developing solution. . Preferable examples of such a material include polyvinyl alcohol and partially saponified polyvinyl acetate. Further, 100 parts by weight of the material of the water-soluble resin layer 2 is further mixed with 1 part of ethylene glycol, propylene glycol, or a condensate or derivative thereof for the purpose of improving releasability from the flexible film.
It is also preferable to add 0.001 to 10 parts by weight of one or more species. By doing so, the water-soluble resin layer 2 can be easily peeled from the flexible film.

The water-soluble resin layer 2 is obtained by applying an aqueous solution of 5 to 20% by weight with a bar coater, a roll coater, a curtain flow coater or the like so as to have a dry thickness of 1 to 10 μm. If this thickness is less than 1 μm, poor adhesion may occur, and if it exceeds 10 μm, the resolution tends to deteriorate. When preparing the aqueous solution, a solvent such as methanol, methyl cellosolve, or acetone may be added in consideration of the viscosity of the solution, defoaming, and the like.

The photosensitive resin composition layer 3 is prepared by mixing the above components and optionally adding a solvent to the applicator,
It is applied by a bar coater, a roll coater, a curtain flow coater or the like to a dry thickness of 10 to 100 μm.

The release film 4 is for stably protecting the photosensitive resin composition layer 3 when not in use,
Stripped off when used. Therefore, it is necessary to have an appropriate releasability that does not peel off when not in use and can be easily peeled off when used. As the release film 4 satisfying such a condition, a PET film, a polypropylene film, a polyethylene film or the like having a thickness of 16 to 125 μm coated or baked with silicone is suitable.

FIG. 2 shows a method of engraving using the dry film prepared as described above. In FIG. 1A, the release film 4 of the dry film shown in FIG. 1 is peeled off and turned upside down to be adhered on the engraved material 5. Since the urethane oligomer is added to the photosensitive resin composition layer 3, the adhesion is very good.

Next, in FIG. 2B, the mask pattern 6 is brought into close contact with the water-soluble resin layer 2, and the ultraviolet rays 7 are exposed using a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, an arc lamp, a xenon lamp or the like. Also, in addition to ultraviolet rays, excimer laser, X-ray, electron beam, etc. may be irradiated. When the photopolymerization initiator 2,4,6-trimethylbenzoyldiphenylphosphine oxide according to the present invention is used, the exposure range is wide (that is, the dimensional accuracy is high or low). Since there is no difference in blast resistance), the resolution is high and workability is good. After this exposure, the mask pattern 6 is removed and development is performed.

FIG. 3C shows the state after development. By the development, the UV non-exposed portion of the water-soluble resin layer 2 and the photosensitive resin composition layer 3 is removed, and only the resin layer 8 of the exposed portion remains. As the developer used for this development, a general-purpose alkaline developer can be used. Examples of alkali components used in the developing solution include lithium, sodium, hydroxides of alkali metals such as potassium,
Carbonates, bicarbonates, phosphates, pyrophosphates, primary amines such as benzylamine, butylamine, secondary amines such as dimethylamine, dibenzylamine, diethanolamine, trimethylamine, triethylamine, triethanolamine, etc. Tertiary amines, morpholine, piperazine, piperidine, cyclic amines such as pyridine, polyamines such as ethylenediamine, hexamethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylbenzylammonium hydroxide, etc. Ammonium hydroxides,
Examples thereof include sulfonium hydroxides such as trimethylsulfonium hydroxide, diethylmethylsulfonium hydroxide, and dimethylbenzylsulfonium hydroxide, choline, and a silicate-containing buffer solution.

When the photosensitive resin composition of the present invention is used, the pattern profile of the resin layer 8 formed after exposure and development becomes good (without trailing). Further resin layer 8
Since it has high adhesion to the material to be engraved 5, even if it is a fine pattern, it does not peel off, and the accuracy of engraving during sandblasting becomes high.

FIG. 3D shows the state after sandblasting. Since the resin layer 8 has higher abrasion resistance than the conventional dry film, the resin layer 8 is not worn away before the engraving of the intended depth is completed. Finally, the resin layer 8
Is peeled off with an alkaline aqueous solution to complete the engraved product shown in FIG.

[0026]

By using the photosensitive resin composition or the photosensitive laminated film for sandblasting of the present invention, the resolution of the pattern and the adhesion to the engraved material are improved, the allowable range of the exposure amount is expanded, and Increased wear resistance during sandblasting.

[0027]

EXAMPLES Examples according to the present invention will be described below. Examples 1 to 8 UV-3000B K8 which is a urethane acrylate having a urethane bond in the molecule and having an acrylic group at the end.
0 (manufactured by Nippon Synthetic Chemistry; containing 20% by weight of methyl ethyl ketone) was mixed with 60 parts by weight of a 25% by weight solution of cellulose phthalate acetate (manufactured by Wako Pure Chemical Industries, Ltd .; trade name KC-71) in 25% by weight of methyl ethyl ketone. , 4,
2 parts by weight of 6-trimethylbenzoyldiphenylphosphine oxide, 0.005 parts by weight of N-nitrosophenylhydroxylamine aluminum salt, oil blue 613
(Orient Chemical) 0.1 part by weight was added and dissolved to prepare the photosensitive resin composition of the present invention.

Separately, 0.5 part by weight of polyethylene glycol (average molecular weight 400) was added to 10 parts of a 10% solution of polyvinyl alcohol (manufactured by Kuraray; trade name PVA-405; saponification degree 80 mol%, polymerization degree 500). The water-soluble resin solution that had been stirred and mixed was applied onto a PET film having a thickness of 75 μm using a bar coater so that the film thickness after drying was 5 μm to form a water-soluble resin layer.

Further, the above-mentioned photosensitive resin composition was applied to this by using an applicator so that the film thickness after drying was 50 μm to form a photosensitive resin composition layer, which was then silicone-coated to 40 μm. The polyethylene film was laminated with a rubber roller so that no bubbles remained, and the film-shaped photosensitive resin according to the present invention was completed. Similarly, a film having a film thickness after drying of 100 μm was also prepared.

The polyethylene film layer of the obtained film-shaped photosensitive resin was peeled off, and the exposed photosensitive resin composition layer was laminated on a glass surface warmed to 80 ° C. with a rubber roller to remove the PET film. To expose the water-soluble resin layer. 200, 150, 1 in this water-soluble resin layer
A test pattern mask having a line width of 25, 100, 80, 70, 60, 50 and 40 μm is brought into close contact with it, and 50, 100, 150 and 200 mJ / c by an ultra-high pressure mercury lamp.
UV exposure was carried out at a dose of m ² . Then the liquid temperature is 25
1.2 kg / c with 0.2% Na ₂ CO ₃ aqueous solution at ℃
Spray development was carried out at an injection pressure of m ² for a film thickness of 50 μm for 70 seconds and for 100 μm for 120 seconds.

Adhesion / resolution (line / spa) at each film thickness
ce) is shown in (Table 1). Here, “adhesion” means the above 20
0, 150, 125, 100, 80, 70, 60, 50
In addition, among the resin layers formed with a line width of 40 μm, the peeling resistance value at 20 ° C. is 300 g / cm ² or more, which is the thinnest line width value. The smaller the value, the better the adhesion. Represent. Further, "resolution" indicates a value of the thinnest line width that does not contact an adjacent line, and a smaller value indicates higher resolution.

[0032]

[Table 1]

Comparative Examples 1 to 8 The same as Examples 1 to 8 except that 2 parts by weight of 2,4,6-trimethylbenzoyldiphenylphosphine oxide of Examples 1 to 8 was changed to 4 parts by weight of dimethylbenzyl ketal. The adhesion / resolution was examined. The results are also shown in (Table 1).

From the results shown in (Table 1), the resin layers of Examples according to the present invention had an exposure dose of 50 to 200 mJ / cm ^2.
It is clear that the adhesion and the resolution are excellent over a wide range. On the other hand, regarding the resin layer of the comparative example using another photopolymerization initiator, when the resin layer thickness is 100 μm,
Although the adhesiveness was almost the same as that of the example, the values of the adhesiveness in other ranges and the resolutions in all ranges were much lower than those of the examples.

Examples 9 and 10 and Comparative Examples 9 and 10 Films of 50 μm thickness and 100 μm thickness formed in the same manner as in Example 1 and Comparative Example 1 were laminated on a glass surface heated to 80 ° C. using a rubber roller. Then, the PET film was removed to expose the water-soluble resin layer. And 50μ
m The thickness of the things 100 mJ / cm ^2, and 100μm solid exposure at 200 mJ / cm ² for one thickness (overall exposure), using abrasive SiC # 600 this, nozzle distance 100 mm, blasting pressure 5 kg / cm ^The nozzle position was fixed at ² and sand blasting was performed to measure the time until the resin layer was worn and disappeared. The results are shown in (Table 2).

[0036]

[Table 2]

As is clear from (Table 2), the resin layer according to the present invention had about 2-3 times as much abrasion resistance as that of the comparative example. Incidentally, when the abrasion time of the resin layer by sandblast is plotted against the film thickness of the resin layer in Examples 9 and 10, a curve as shown in FIG. 3 is drawn. By creating a curve like the one in the figure, when the required blast resistance time is determined according to the desired etching depth, the film thickness to be formed can be determined in accordance with this blast resistance time. It is convenient and convenient.

Examples 11 to 34 and Comparative Examples 11 to 34 A 50 μm thick film formed in the same manner as in Example 1 and Comparative Example 1 was laminated on a glass surface heated to 80 ° C. using a rubber roller, and PET was used. The film was removed to expose the water-soluble resin layer. And 40, 50, 100, 1
Solid exposure (overall exposure) was performed at 50, 200, and 220 mJ / cm ² , and this was sandblasted by using a polishing agent SiC # 600 and fixing the nozzle position with a nozzle distance of 100 mm and a blast pressure of 5 kg / cm ² to form a resin layer. The time until it was worn and disappeared was measured. Further in 200 mJ / cm ² for a film of 50μm thickness, those for a 100μm thick film was post-exposed at 400 mJ / cm ^2,
The post-exposure and subsequent post-baking at 150 ° C. for 20 minutes, and the post-baking-only post-exposure were similarly subjected to a sandblasting abrasion test. These results (Table 3), (Table 4), (Table 5) and (Table 6)
Shown in.

[0039]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

Further, FIG. 4 shows an example without post-exposure and post-baking (that is, Examples 11 to 16; line segment A), the same comparative example (that is, Comparative Examples 11 to 16; line segment a), and post-exposure. Examples with only (that is, Examples 17 to 22; line segment B), same comparative examples (that is, Comparative Examples 17 to 22; line segment b), examples with both post-exposure and post-baking (that is, implementation) Examples 23-2
8; line segment C), the same comparative example (ie, comparative examples 23 to 28; line segment c), and an example with only post-baking (ie,
The numerical values of Examples 29 to 34; line segment D) and the same comparative example (that is, comparative examples 29 to 34; line segment d) were plotted.

In FIG. 4, the maximum value of the resin layer wear time of the line segment a of the comparative example is 40 seconds (exposure amount 100 mJ / cm 2).
The ratios of the line segments A to D of each example to ² ) are 2.6 times A / a, 3.2 times B / a, 2.8 times C / a, and 4. It was 6 times. B / b is 1.8 times, C
/ C was 1.6 times and D / d was 3.8 times, and the durability time of the execution was longer than that of the comparative example. Also, from the figure, the resin layer of the example is different from the comparative example in the exposure amount of 50 to 200 m.
It is also clear that it has high blast resistance in a wide range of J / cm ² .

[0042]

As described above, by using the photosensitive resin composition of the present invention, the pattern profile of the photo-cured resin layer becomes good, so that highly accurate engraving can be performed. Moreover, since the allowable range of the exposure amount is wide, the resolution is high and the workability is also improved. Furthermore, since the blast resistance of the resin layer is significantly improved, the amount of the photosensitive resin composition used can be reduced and highly accurate engraving can be performed.

Further, by using the dry film of the present invention, in addition to the above-mentioned various effects, the adhesion with the mask pattern is good, so that the resolution is improved and the adhesion with the engraved material is also good. Therefore, even a fine pattern is not peeled off, and the precision of engraving during sandblasting becomes high.

[Brief description of drawings]

FIG. 1 is a sectional view showing an example of a dry film of the present invention.

FIG. 2 is a process drawing showing a method for engraving using the dry film of the present invention.

FIG. 3 Resin layer thickness-resin layer wear time diagram

FIG. 4 Exposure amount-resin layer wear time diagram

[Explanation of symbols]

1 ... Film, 2 ... Water-soluble resin layer, 3 ... Photosensitive resin composition layer, 4 ... Release film, 5 ... Engraved material, 8 ... Resin layer.

Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location G03F 7/029 7/11

Claims (2)

[Claims] 1. A photosensitive resin composition for sandblasting, which comprises a urethane oligomer having an ethylenically unsaturated double bond at its end, and a cellulose derivative or a compound containing an ethylenically unsaturated double bond, which is used as a photopolymerization initiator. A photosensitive resin composition comprising 4,6-trimethylbenzoyldiphenylphosphine oxide. 2. A photosensitive laminated film for sandblasting, wherein a water-soluble resin layer, a photosensitive resin composition layer and a release film are laminated in this order on a flexible film, wherein the photosensitive resin composition layer is a terminal. A laminated film comprising a urethane oligomer having an ethylenically unsaturated double bond, a cellulose derivative, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide as a photopolymerization initiator.